Probing high-lying N2 ++ and CO++ states via energy-selective fragment spectra

Dissociation of molecular ions from highly excited states is difficult to probe, so our knowledge of their dynamical evolution and the parameters governing the dissociation is limited. The main complication is due to the large density of high-lying states and crossing of states. The latter may change the kinematics of the fragments, but in general, the contributions from different states to the fragment kinetic energy distributions cannot be separated. Consequently, the exact nature of the evolution remains elusive. In the present work, we have performed kinematic analysis of the dissociation dynamics of di-cations of N2 and CO formed by photoionization, aiming to probe their highly excited states. Correlated fragment ion momenta are measured in coincidence with energy-analyzed ejected electrons, allowing us to estimate energy of the transient molecular ions. These measurements bring out the differences in kinematics of the fragmentation of transient molecular ions having different internal energies. Our analysis indicates that highly excited states decay primarily to their own asymptotic limits with only weak coupling to states decaying to lower asymptotes.